Recent Advances in 4D Printing of Advanced Materials and Structures for Functional Applications.

4D printing has attracted tremendous worldwide attention during the past decade. This technology enables the shape, property, or functionality of printed structures to change with time in response to diverse external stimuli, making the original static structures alive. The revolutionary 4D-printing technology offers remarkable benefits in controlling geometric and functional reconfiguration, thereby showcasing immense potential across diverse fields, including biomedical engineering, electronics, robotics, and photonics. Here, a comprehensive review of the latest achievements in 4D printing using various types of materials and different additive manufacturing techniques is presented. The state-of-the-art strategies implemented in harnessing various 4D-printed structures are highlighted, which involve materials design, stimuli, functionalities, and applications. The machine learning approach explored for 4D printing is also discussed. Finally, the perspectives on the current challenges and future trends toward further development in 4D printing are summarized.

Electric Power Generated from Magnetic Nanofluid Droplets Sliding upon Superslippery Surfaces.

An enduring challenge in the field of electric power generation employing magnetic nanofluids pertains to the inherent issue of solid-liquid adhesion, which results in random residue deposition of magnetic nanofluids on solid substrates during motion. Superslippery surfaces, characterized by their exceptional repellent properties and ultralow adhesion characteristics toward an extensive spectrum of fluids, offer an effective approach to ameliorate the aforementioned adhesive problem. Herein, it is demonstrated that electric power can be generated through the sliding of magnetic nanofluid droplets on superslippery surfaces. The electric power generation can be attributed to the change in magnetic flux caused by the magnetic nanofluid droplet passing or leaving a bottom coil associated with a magnet. By tailoring system parameters, such as the volume of the magnetic nanofluid or the vibration speed, the resulting maximal current can exceed 6 µA. An integrated device, featuring enclosed superslippery inner surfaces, can be securely attached to the arm of a volunteer, allowing for the conversion of mechanical energy into electricity. When the volunteer's arm moves, the electrical energy generated by the device can be utilized to light an LED lamp bead. The proposed strategy using superslippery surfaces facilitates low-adhesion transport of magnetic nanofluids, presenting an alternative solution to the development of next-generation solid/liquid energy harvesting devices.

In Situ 4D Printing of Polyelectrolyte/Magnetic Composites for Sutureless Gastric Perforation Sealing.

In situ bioprinting has emerged as one of the most promising techniques for the sutureless tissue sealing of internal organs. However, most existing in situ bioprinting methods are limited by the complex and confined printing space inside the organs, harsh curing conditions for printable bioinks, and poor ability to suturelessly seal injured parts. The combination of in situ bioprinting and 4D printing is a promising technique for tissue repair. Herein, the in situ 4D printing of polyelectrolyte/magnetic composites by gastroscopy for sutureless internal tissue sealing is reported. Using gastric perforation as an example, a gelatin/sodium alginate/magnetic bioink is developed, which can be precisely located by a gastroscope with the assistance of an external magnetic field, solidified in gastric fluid, and firmly adhered to tissue surfaces. The solidified bioink along the defect can be attracted by an external magnetic field, resulting in sutureless sealing. A demonstration using a porcine stomach with an artificial perforation confirms the feasibility of sutureless sealing using 4D printing. Moreover, an in vivo investigation on gastric perforation in a rat model identifies the biocompatibility by H&E and CD68+ staining. This study provides a new orientation and concept for functionality-modified in situ 4D bioprinting.

Additively Manufactured Flexible Liquid Metal-Coated Self-Powered Magnetoelectric Sensors with High Design Freedom.

Although additive manufacturing enables controllable structural design and customized performance for magnetoelectric sensors, their design and fabrication still require careful matching of the size and modulus between the magnetic and conductive components. Achieving magnetoelectric integration remains challenging, and the rigid coils limit the flexibility of the sensors. To overcome these obstacles, this study proposes a composite process combining selective laser sintering (SLS) and 3D transfer printing for fabricating flexible liquid metal-coated magnetoelectric sensors. The liquid metal forms a conformal conductive network on the SLS-printed magnetic lattice structure. Deformation of the structure alters the magnetic flux passing through it, thereby generating voltage. A reverse model segmentation and summation method is established to calculate the theoretical magnetic flux. The impact of the volume fraction, unit size, and height of the sensors on the voltage is studied, and optimization of these factors yields a maximum voltage of 45.6 µV. The sensor has excellent sensing performance with a sensitivity of 10.9 kPa-1 and a minimum detection pressure of 0.1 kPa. The voltage can be generated through various external forces. This work presents a significant advancement in fabricating liquid metal-based magnetoelectric sensors by improving their structural flexibility, magnetoelectric integration, and design freedom.

Multimaterial 3D and 4D Bioprinting of Heterogenous Constructs for Tissue Engineering.

Additive manufacturing (AM), which is based on the principle of layer-by-layer shaping and stacking of discrete materials, has shown significant benefits in the fabrication of complicated implants for tissue engineering (TE). However, many native tissues exhibit anisotropic heterogenous constructs with diverse components and functions. Consequently, the replication of complicated biomimetic constructs using conventional AM processes based on a single material is challenging. Multimaterial 3D and 4D bioprinting (with time as the fourth dimension) has emerged as a promising solution for constructing multifunctional implants with heterogenous constructs that can mimic the host microenvironment better than single-material alternatives. Notably, 4D-printed multimaterial implants with biomimetic heterogenous architectures can provide a time-dependent programmable dynamic microenvironment that can promote cell activity and tissue regeneration in response to external stimuli. This paper first presents the typical design strategies of biomimetic heterogenous constructs in TE applications. Subsequently, the latest processes in the multimaterial 3D and 4D bioprinting of heterogenous tissue constructs are discussed, along with their advantages and challenges. In particular, the potential of multimaterial 4D bioprinting of smart multifunctional tissue constructs is highlighted. Furthermore, this review provides insights into how multimaterial 3D and 4D bioprinting can facilitate the realization of next-generation TE applications.

Evaluation of mechanical and biological properties of akermanite/poly-ether-ether- ketone composite fabricated by high- temperature laser powder bed fusion.

High-temperature laser bed powder fusion (HT-LPBF) technology is an ideal method for processing poly-ether-ether-ketone (PEEK) implants with personalized bionic structures, but the biological inertia of PEEK limits its medical applications. In this study, we evaluated the mechanical and biological properties of a novel akermanite (AKM)/PEEK composite for HT-LPBF. The results showed that tiny AKM particles are evenly attached to the surface of the PEEK particle. The delayed peak crystallization temperature and stable sintering window ensure the processing feasibility of the AKM/PEEK composites. The tensile strength and Young's modulus are in the range of 30.83-98.73 MPa and 2.27-3.71 GPa, respectively, which can match the properties of cancellous bones and meet their implanting requirement. The CCK-8 experiments demonstrated the biocompatibility of the composites and the good proliferation of bone marrow stromal cells. The dense hydroxyapatite network layer and petal-like hydroxyapatite demonstrates biological activity, indicating that the composite has a good potential in the orthopedics fields.

Superhydrophobic/Superhydrophilic Janus Evaporator for Extreme High Salt-Resistance Solar Desalination by an Integrated 3D Printing Method.

The emerging solar desalination technology has incomparable advantages for providing a clean water solution. However, the issue of salt accumulation on the solar evaporator tops during the steam generation leads to a considerable decrease in the evaporation rate. Herein, we demonstrate a superhydrophobic/superhydrophilic Janus evaporator that enables a stable solar evaporation even in saturated brine. Our Janus solar evaporator with a superhydrophobic top and a superhydrophilic bottom has been manufactured integrally, allowing for a fast steam evaporation without the impediment of the accumulated salt residues. The superhydrophobic top changes the water passageway from the center toward the edges while it allows for the vertical transport of both solar thermo and evaporated steams. Salt residues would only be deposited at the edges of the superhydrophilic bottom, allowing for a long-term stability of the evaporator for a continuous (>50 h) solar evaporation in saturated brine, which is record-breaking for salt-resistant solar evaporators. With stable and efficient evaporation performance out of high-salinity brine, this work provides a fascinating avenue for the desalination of seawater in a salt-resistant and efficient manner.

Large-Scale, Abrasion-Resistant, and Solvent-Free Superhydrophobic Objects Fabricated by a Selective Laser Sintering 3D Printing Strategy.

Manufacturing abrasion-resistant superhydrophobic matters is challenging due to the fragile feature of the introduced micro-/nanoscale surface roughness. Besides the long-term durability, large scale at meter level, and 3D complex structures are of great importance for the superhydrophobic objects used across diverse industries. Here it is shown that abrasion-resistant, half-a-meter scaled superhydrophobic objects can be one-step realized by the selective laser sintering (SLS) 3D printing technology using hydrophobic-fumed-silica (HFS)/polymer composite grains. The HFS grains serve as the hydrophobic guests while the sintered polymeric network provides the mechanical strength, leading to low-adhesion, intrinsic superhydrophobic objects with desired 3D structures. It is found that as-printed structures remained anti-wetting capabilities even after undergoing different abrasion tests, including knife cutting test, rude file grinding test, 1000 cycles of sandpaper friction test, tape test and quicksand impacting test, illustrating their abrasion-resistant superhydrophobic stability. This strategy is applied to manufacture a shell of the unmanned aerial vehicle and an abrasion-resistant superhydrophobic shoe, showing the industrial customization of large-scale superhydrophobic objects. The findings thus provide insight for designing intrinsic superhydrophobic objects via the SLS 3D printing strategy that might find use in drag-reduce, anti-fouling, or other industrial fields in harsh operating environments.

Low intensity near-infrared light promotes bone regeneration via circadian clock protein cryptochrome 1.

Bone regeneration remains a great clinical challenge. Low intensity near-infrared (NIR) light showed strong potential to promote tissue regeneration, offering a promising strategy for bone defect regeneration. However, the effect and underlying mechanism of NIR on bone regeneration remain unclear. We demonstrated that bone regeneration in the rat skull defect model was significantly accelerated with low-intensity NIR stimulation. In vitro studies showed that NIR stimulation could promote the osteoblast differentiation in bone mesenchymal stem cells (BMSCs) and MC3T3-E1 cells, which was associated with increased ubiquitination of the core circadian clock protein Cryptochrome 1 (CRY1) in the nucleus. We found that the reduction of CRY1 induced by NIR light activated the bone morphogenetic protein (BMP) signaling pathways, promoting SMAD1/5/9 phosphorylation and increasing the expression levels of Runx2 and Osterix. NIR light treatment may act through sodium voltage-gated channel Scn4a, which may be a potential responder of NIR light to accelerate bone regeneration. Together, these findings suggest that low-intensity NIR light may promote in situ bone regeneration in a CRY1-dependent manner, providing a novel, efficient and non-invasive strategy to promote bone regeneration for clinical bone defects.

Multi-Material Additively Manufactured Magnetoelectric Architectures with a Structure-Dependent Mechanical-to-Electrical Conversion Capability.

Multi-material additive manufacturing has become a promising trend in fabricating advanced functional architectures due to its controllable design of diverse material species and novel structures. It remains challenging to endow the multi-material components with a mechanical-to-electrical conversion capability. This study reports on multi-material selectively laser sintered magnetoelectric architectures that can convert mechanical energy to electricity in a structure-dependent manner. The principal aim is to establish a relationship between the electrical output and the printed structures by fabricating a series of porous architectures with diverse structural parameters. The findings show that the output voltage increases with the decrease of the elastic modulus and the increase of the magnetic height, which has been analyzed by numerical simulation. Owing to the mechanical-to-electrical conversion capability, a pair of multi-material printed sneakers with the functionalities of power generation and gait analysis has been prepared. The voltage output reaches as high as ≈2 V, which can lighten a light-emitting diode lamp when a user is running. The described solution in this work has offered an exploration framework for the design, fabrication, and application prospects of multi-material additively manufactured architectures.

A Superconducting-Material-Based Maglev Generator Used for Outer-Space.

Solar cells are conventionally used to harvest energy in outer space, but they are ineffective in dark locations. Here, it is shown that superconducting materials-which work best in cold environments, such as those found in outer space-provide a mechanism to harvest energy that does not require light. A superconducting magnetic levitation (maglev) magnetoelectric generator (SMMG) can convert mechanical impacts to electricity at its working temperature <90 K. The SMMG device consists of a permanent magnet, a conductive coil, and a superconducting layer (SL). Owing to the existence of the SL, the permanent magnet levitates over the SL and rapidly returns to an equilibrium height after being displaced by a mechanical impact. The impact changes the gap between the levitated magnet and the coil, resulting in a variation in magnetic flux that induces electrical current in the coil. Thus, the SMMG converts low-frequency (<3.7 Hz) mechanical energy to electricity. The output maximum peak voltage, peak power, and peak power density of the SMMG are 4.3 V, 35 mW, and 17.8 W m-2 , respectively, with a load resistance of 300 Ω. The SMMG can charge a capacitor of 10 000 µF to 3.8 V with a continuous impact, which is sufficient to power critical wireless communication. The superconductor works best in cold environments and therefore is well-suited for providing electricity to sensors and communication devices in outer space, particularly in places where the sun may not reach.

Enhanced Photocatalysis of Black TiO2/Graphene Composites Synthesized by a Facile Sol-Gel Method Combined with Hydrogenation Process.

In this study, in situ TiO2 was grown on the surface of graphene by a facile sol-gel method to form black TiO2/graphene composites with highly improved photocatalytic activity. The combination of graphene and TiO2 was beneficial to eliminate the recombination of photogenerated electron holes. The self-doping Ti3+ was introduced, accompanied by the crystallization of amorphous TiO2, during the hydrogenation process. Consequently, the narrowed bandgap caused by self-doping Ti3+ enhanced the visible light absorption and thus made the composites appear black. Both of them improved the photocatalytic performance of the synthesized black TiO2/graphene composites. The band structure of the composite was analyzed by valence band XPS, revealing the reason for the high visible light catalytic performance of the composite. The results proved that the black TiO2/graphene composites synthesized show attractive potential for applications in environmental and energy issues.

Three-dimensional printing of gyroid-structured composite bioceramic scaffolds with tuneable degradability.

Customisation of bioactivity and degradability of porous bioceramic scaffolds is a formidable challenge in the field of regenerative medicine. In this study, we developed gyroid-structured ternary composite scaffolds (biphasic calcium phosphate (BCP) and 45S5 bioglass® (BG)) using digital light processing 3D printing technology based on material and structural design. Additionally, the mechanical strength, bioactivity, degradability, and biocompatibility of the composite ceramic scaffolds were evaluated. The results revealed that BG reacted with BCP to generate major active crystalline phases of CaSiO3 and Na3Ca6(PO4)5. These active crystalline phases accelerated the exchange rate of Si4+, Ca2+, and PO43- with HCO3- in simulated body fluids and resulted in the rapid formation of carbonated hydroxyapatite (CHA), analogous to the formation of natural bone tissue. Interestingly, the precipitated CHA showed petal- and needle-like morphologies, which provided a large surface area to promote cell adhesion and proliferation. Furthermore, an increase in the BG content improved the degradability of ternary composite scaffolds after soaking in Tris-HCl solution. The tuneable degradability increased by three times at 30 wt% BG and sharply increased by 6.8 times at 40 wt% BG. This study provides a promising strategy to design scaffolds with improved bioactivity and tuneable degradability to assist a diverse population suffering from orthopedic conditions.

Recent Advances on High-Performance Polyaryletherketone Materials for Additive Manufacturing.

Polyaryletherketone (PAEK) is emerging as an important high-performance polymer material in additive manufacturing (AM) benefiting from its excellent mechanical properties, good biocompatibility, and high-temperature stability. The distinct advantages of AM facilitate the rapid development of PAEK products with complex customized structures and functionalities, thereby enhancing their applications in various fields. Herein, the recent advances on AM of high-performance PAEKs are comprehensively reviewed, concerning the materials properties, AM processes, mechanical properties, and potential applications of additively manufactured PAEKs. To begin, an introduction to fundamentals of AM and PAEKs, as well as the advantages of AM of PAEKs is provided. Discussions are then presented on the material properties, AM processes, processing-matter coupling mechanism, thermal conductivity, crystallization characteristics, and microstructures of AM-processed PAEKs. Thereafter, the mechanical properties and anisotropy of additively manufactured PAEKs are discussed in depth. Their representative applications in biomedical, aerospace, electronics, and other fields are systematically presented. Finally, current challenges and possible solutions are discussed for the future development of high-performance AM polymers.

Simultaneous strength and ductility enhancements of high thermal conductive Ag7.5Cu alloy by selective laser melting.

High electrical and thermal conductive metals (HETCM) play a key role in smart electronics, green energy, modern communications and healthcare, however, typical HETCM (e.g., Ag, Au, Cu) usually have relatively low mechanical strength, hindering further applications. Selective laser melting (SLM) is a potentially transformative manufacturing technology that is expected to address the issue. Ag is the metal with the highest thermal conductivity, which induces microscale grain refinement, but also leads to high internal stresses by SLM. Here, we select Ag7.5Cu alloy as an example to demonstrate that multi-scale (micro/meso/macro) synergies can take advantage of high thermal conductivity and internal stresses to effectively strengthen Ag alloy. The mimicry of metal-hardened structures (e.g., large-angle boundary) is extended to the mesoscale by controlling the laser energy density and laser scanning strategy to manipulate the macroscale internal stress intensity and mesoscale internal stress direction, respectively, to form mesoscale large-angle "grains", resulting in multiple mutual perpendicular shear bands during fracture. The presented approach achieved a significant enhancement of yield strength (+ 145%) and ductility (+ 28%) without post-treatment. The results not only break the strength-ductility trade-off of conventional SLM alloys, but also demonstrate a multi-scale synergistic enhancement strategy that exploits high thermal conductivity and internal stresses.

3D-Printed Anisotropic Polymer Materials for Functional Applications.

Anisotropy is the characteristic of a material to exhibit variations in its mechanical, electrical, thermal, optical properties, etc. along different directions. Anisotropic materials have attracted great research interest because of their wide applications in aerospace, sensing, soft robotics, and tissue engineering. 3D printing provides exceptional advantages in achieving controlled compositions and complex architecture, thereby enabling the manufacture of 3D objects with anisotropic functionalities. Here, a comprehensive review of the recent progress on 3D printing of anisotropic polymer materials based on different techniques including material extrusion, vat photopolymerization, powder bed fusion, and sheet lamination is presented. The state-of-the-art strategies implemented in manipulating anisotropic structures are highlighted with the discussion of material categories, functionalities, and potential applications. This review is concluded with analyzing the current challenges and providing perspectives for further development in this field.

3D Printing and Chemical Dealloying of a Hierarchically Micro- and Nanoporous Catalyst for Wastewater Purification.

Hierarchically porous-structured materials show tremendous potential for catalytic applications. In this work, a facile method through the combination of three-dimensional (3D) printing and chemical dealloying was employed to synthesize a nanoporous-copper-encapsulating microporous-diamond-cellular-structure (NPC@DCS) catalyst. The developed NPC@DCS catalyst was utilized as a heterogeneous photo-Fenton-like catalyst where its catalytic applications in the remediation of organic wastewater were exemplified. The experimental results demonstrated that the NPC@DCS catalyst possessed a remarkable degradation efficiency in the removal of rhodamine B with a reaction rate of 8.24 × 10-2 min-1 and displayed attractive stability, durability, mineralization capability, and versatility. This work not only manifests the applicability of the proposed NPC@DCS catalyst for wastewater purification in practical applications but also is anticipated to inspire the incorporation of the 3D printing technology and chemical synthesis to design high-performance metal catalysts with tunable hierarchical micro- and nanopores for functional applications.

Research Status and Prospect of Additive Manufactured Nickel-Titanium Shape Memory Alloys.

Nickel-titanium alloys have been widely used in biomedical, aerospace and other fields due to their shape memory effect, superelastic effect, as well as biocompatible and elasto-thermal properties. Additive manufacturing (AM) technology can form complex and fine structures, which greatly expands the application range of Ni-Ti alloy. In this study, the development trend of additive manufactured Ni-Ti alloy was analyzed. Subsequently, the most widely used selective laser melting (SLM) process for forming Ni-Ti alloy was summarized. Especially, the relationship between Ni-Ti alloy materials, SLM processing parameters, microstructure and properties of Ni-Ti alloy formed by SLM was revealed. The research status of Ni-Ti alloy formed by wire arc additive manufacturing (WAAM), electron beam melting (EBM), directional energy dedication (DED), selective laser sintering (SLS) and other AM processes was briefly described, and its mechanical properties were emphatically expounded. Finally, several suggestions concerning Ni-Ti alloy material preparation, structure design, forming technology and forming equipment in the future were put forward in order to accelerate the engineering application process of additive manufactured Ni-Ti alloy. This study provides a useful reference for scientific research and engineering application of additive manufactured Ni-Ti alloys.

Selective Laser Sintering-Based 4D Printing of Magnetism-Responsive Grippers.

Components fabricated by four-dimensional (4D) printing hold the potential for applications in soft robotics because of their characteristics of responding to external stimuli. Grippers, being the common structures used in robotics, were fabricated by the selective laser sintering (SLS)-based 4D printing of magnetism-responsive materials and tested for remote-controllable deformation in an external magnetic field. A composite material consisting of magnetic Nd2Fe14B powder and thermoplastic polyurethane powder was selected as the raw material for the SLS; the magnetic particle acquired permanent magnetism by magnetization after the SLS process. Microscopic characterization showed the homogeneous dispersion of magnetic particles inside the polymer matrix. The magnetic induction intensity distribution was systematically investigated by both experiments and numerical simulations. The reliability of the numerical model proposed was justified by the excellent consistency between them. The deformation of the grippers could be regulated by tuning the magnetic particle content and the distance from the external magnet; the deformation mechanism is investigated numerically. The magnetic driving force and the corresponding horizontal displacement are calculated, thus having high accuracy compared with the existing research that obtained the deformation amount by only visual inspection. Mechanical properties of the SLS-fabricated magnetic polymer composite specimens were also studied because of their close relationship with the deformation behaviors. These findings provide guidance for future research on controllable deformation and driving force calculation for 4D printing.

4D Printing Strain Self-Sensing and Temperature Self-Sensing Integrated Sensor-Actuator with Bioinspired Gradient Gaps.

Integrated sensor-actuators with exciting functionalities, such as action self-sensing, position self-sensing, posture self-sensing, or active sensing, are promising for applications in biomedical device, human-machine interaction, intelligent self-protection devices, and humanoid robots. Despite recent progress, it remains challenging to achieve a macroscopical integrated sensor-actuator in a material system with microstructures. To address this critical challenge, a 4D printing bioinspired microstructure strategy is reported to design a high-performance integrated sensor-actuator capable of simultaneous actuation and sensation. Decoupled thermal stimulation and strain sensation is achieved by combining nanocarbon black/polylactic acid composites with bioinspired gradient microgap structures. As a result, printed integrated sensor-actuators can actively touch objects triggered by thermal stimulation and self-sense the touching state through the resistance change. It is anticipated that the basic design principle underlying this behavior can be used to develop integrated sensor-actuators of various shapes and functionalities to meet desirable applications.